4-imino-n-alkoxy or oxy-polyalkyl-piperidine compounds and their use as polymerization regulators

ABSTRACT

The present invention relates to selected 4-imino-N-alkoxy-polyalkyl-peperidine compounds preparation, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a 4-imino-N-alkoxy-polyalkyl-piperidine compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of 4-imino-N-alkoxy-polyalkyl-piperidine compounds for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator, as well as a process for polymerization are also subjects of the present invention

The present invention relates to selected4-imino-N-alkoxy-polyalkyl-piperidine compounds, a polymerizablecomposition comprising a) at least one ethylenically unsaturated monomerand b) a 4-imino-N-alkoxy-polyalkyl-piperidine compound. Further aspectsof the present invention are a process for polymerizing ethylenicallyunsaturated monomers, and the use of4-imino-N-alkoxy-polyalkyl-piperidine compounds for controlledpolymerization. The intermediate N-oxyl derivatives, a composition ofthe N-oxyl derivatives with ethylenically unsaturated monomers and afree radical initiator, as well as a process for polymerization are alsosubjects of the present invention.

The compounds of the present invention provide polymeric resin productshaving low polydispersity. The polymerization process proceeds with goodmonomer to polymer conversion efficiency. In particular, this inventionrelates to stable free radical-mediated polymerization processes whichprovide homopolymers, random copolymers, block copolymers, multiblockcopolymers, graft copolymers and the like, at enhanced rates ofpolymerization and enhanced monomer to polymer conversions.

U.S. Pat. No. 4,581,429 to Solomon et al., issued Apr. 8, 1986,discloses a free radical polymerization process which controls thegrowth of polymer chains to produce short chain or oligomerichomopolymers and copolymers, including block and graft copolymers. Theprocess employs an initiator having the formula (in part) R′R″N—O—X,where X is a free radical species capable of polymerizing unsaturatedmonomers. The reactions typically have low conversion rates.Specifically mentioned radical R′R″N—O. groups are derived from 1,1,3,3tetraethylisoindoline, 1,1,3,3 tetrapropylisoindoline, 2,2,6,6tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine ordi-t-butylamine. However, the suggested compounds do not fulfill allrequirements. particularly the polymerization of acrylates does notproceed fast enough and/or the monomer to polymer conversion is not ashigh as desired.

GB 2335190 firstly discloses polymerization regulators/initiators on thebasis of 4-substituted 2,2,6,6-tetraalkylpiperidine, wherein the alkylgroups have from 1 to 4 carbon atoms and at least one group is differentfrom methyl.

However none of the nitroxide and nitroxylether compounds, in particularnone of those described as regulators/initiators for controlled radicalpolymerization have a 4-imino substitutent.

Surprisingly it has now been found that the 4-imino2,2,6,6-tetraalkylpiperidine derivatives of the present invention are ofparticular industrial value, since they can be prepared in high yieldand purity even considering large production quantities.

The imino structure in 4 position ensures high thermal stability whichis important for storage, particularly at elevated temperatures.

The compounds exhibit an unchanged initiating/regulating activity evenafter storage at elevated temperatures as for example used inconventional stability tests.

Another problem associated with nitroxyl or nitroxyl ether mediated freeradical polymerization is the formation of a significant color of theresulting polymer. The compounds of the present invention which have aimino structure in 4-position impart significantly less color to thepolymer compared to other prior art compounds of similar structure.

In some cases either the end product or at least an intermediate productis of crystalline form and therefore can be easily purified byconventional recrystallization.

The 4-imino group surprisingly leads to slightly higher monomer topolymer conversions in some cases as compared to the corresponding 4-oxogroup.

The steric hindrance introduced by ethyl groups instead of methyl groupsin the 2 and/or 6 position further leads to an increased initiatingactivity and control of polymerization.

Furthermore, when the 4-hydroxylamine substitution is left as such, itis possible to react the OH group, when the polymer is already formed,to produce telechelics.

One subject of the invention is a compound of formula (I)

-   G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂ together    and G₃ and G₄ together, or G₁ and G₂ together or G₃ and G₄ together    are pentamethylene; wherein, when G₁, G₂, G₃ and G₄ are C₁–C₄alkyl,    at least one is higher alkyl than methyl; G₅ and G₆ are each    independently of the other hydrogen or C₁–C₄alkyl;-   n is 1, 2, 3, or 4-   Y is O, NR₂ or when n is 1 and R₁ represents alkyl or aryl Y is    additionally a direct bond; R₂ is H, C₁–C₁₈alkyl or phenyl;-   if n is 1-   R₁ is H, straight or branched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or    C₃–C₁₈alkinyl, which unsubstituted or substitued, by one or more OH,    C₁–C₈alkoxy, carboxy, C₁–C₈alkoxycarbonyl;-   C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;-   phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or    substituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy,    carboxy, C₁–C₈alkoxycarbonyl;-   —C(O)—C₁–C₃₆alkyl, or an acyl moiety of α,β-unsaturated carboxylic    acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid    having 7 to 15 carbon atoms;-   —SO₃ ⁻Q⁺, —PO(O⁻Q⁺)₂, —P(O)(OR₂)₂, —SO₂—R₂, —CO—NH—R₂, —CONH₂,    COOR₂, or Si(Me)₃, wherein Q⁺ is H⁺, ammnonium or an alkali metal    cation;-   if n is 2-   R₁ is C₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which    may be unsubsti substitued, by one or more OH, C₁–C₈alkoxy, carboxy,    C₁–C₈alkoxycarbonyl;-   or xylylene; or-   R₁ is a bisacyl radical of an aliphatic dicarboxylic acid having 2    to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic    acid having 8–14 carbon atoms;-   if n is 3,-   R₁ is a trivalent radical of an aliphatic, cycloaliphatic or    aromatic tricarboxylic acid;-   if n is 4, R₁ is a tetravalent radical of an aliphatic,    cycloaliphatic or aromatic tetracarboxylic acid; and-   X is selected from the group consisting of-   —CH-aryl,

-    —CH₂—CH₂-aryl,

-    (C₅–C₆cycloalkyl)₂CCN, (C₁–C₁₂alkyl)₂CCN, —CH₂CH═CH₂,    (C₁–C₁₂)alkyl-CR₂₀—C(O)—(C₁–C₁₂)alkyl,    (C₁–C₁₂)alkyl-CR₂₀—C(O)—(C₆–C₁₀)aryl,    (C₁–C₁₂)alkyl-CR₂₀—C(O)—(C₁–C₁₂)alkoxy,    (C₁–C₁₂)alkyl-CR₂₀—C(O)-phenoxy, (C₁–C₁₂)alkyl-CR₂₀    —C(O)—N-di(C₁–C₁₂)alkyl, (C₁–C₁₂)alky₂₀—CO—NH(C₁–C₁₂)alkyl,    (C₁–C₁₂)alkyl-CR₂₀—CO—NH₂, —CH₂CH═CH—CH₃, —CH₂—C(CH ₃)═CH₂,-   —CH₂—CH═CH-phenyl,

-    3–Cyclohexenyl, 3-cyclopentenyl,

-    wherein-   R₂₀ is hydrogen or C₁–C₁₂alkyl;-   the alkyl groups are unsubstituted or substituted with one or more    —OH, —COOH or —C(O)R₂₀ groups; and-   the aryl groups are phenyl or naphthyl which are unsubstituted or    substituted with C₁–C₁₂alkyl, halogen, C₁–C₁₂alkoxy,    C₁–C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COO(C₁–C₁₂)alkyl.

C₁–C₁₈alkyl can be linear or branched. Examples are methyl, ethyl,propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl,hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl,dodecyl or octadecyl. Where up to C₃₆alkyl is possible, C₁–C₁₈alkyl ispreferred.

Alkyl substituted by a group —COOH is for example CH₂—COOH,CH₂—CH₂—COOH, (CH₂)₃—COOH or CH₂—CHCOOH—CH₂—CH₃

Hydroxyl- or alkoxycarbonyl substituted C₁–C₁₈alkyl can be, for example,2-hydroxyethyl, 2-hydroxypropyl, methoxycarbonylmethyl or2-ethoxycarbonylethyl.

Alkenyl having from 3 to 18 carbon atoms is a branched or unbranchedradical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,isododecenyl.

Alkinyl having from 3 to 18 carbon atoms is a branched or unbranchedradical, for example propinyl, 2-butinyl, 3-butinyl, isobutinyl,n-2,4-pentadiinyl, 3-methyl-2-butinyl, n-2-octinyl, n-2-dodecinyl,isododecinyl.

Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.

C₇–C₉phenylalkyl is for example benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl, benzyl is preferred.

C₅–C₁₂cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl,methylcyclopentyl or cyclooctyl.

C₅–C₁₂cycloalkenyl is for example 3-cyclopentenyl, 3-cyclohexenyl or3-cycloheptenyl.

If R₁ is a monovalent radical of a saturated, unsaturated or aromaticcarboxylic acid, it is, for example, an acetyl, caproyl, stearoyl,acryloyl, methacryloyl, benzoyl orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

If R₁ is a divalent radical of a dicarboxylic acid, it is, for example,a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl,itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl,butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl orbicycloheptenedicarbonyl radical.

If R₁ is a trivalent radical of a tricarboxylic acid, it is, forexample, a trimellitoyl, citryl or nitrilotriacetyl radical.

If R₁ is a tetravalent radical of a tetracarboxylic acid, it is, forexample, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acidor of pyromellitic acid.

Preferably n is 1 or 2 and more preferably n is 1.

Preferably at least one of G₁, G₂, G₃ or G₄ is ethyl or propyl, inparticular ethyl.

Preferably X is selected from the group consisting of

-   —CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅–C₆cycloalkyl)₂CCN,    (CH₃)₂CCN,

-    —CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁–C₈alkyl)CR₂₀—C(O)-phenyl,    (C₁–C₈)alkyl-CR₂₀—C(O)—(C₁–C₈)alkoxy,    (C₁–C₈)alkyl-CR₂₀—C(O)—(C₁–C₈)alkyl,    (C₁–C₈)alkyl-CR₂₀—C(O)—N-di(C₁–C₈)alkyl,    (C₁–C₈)alkyl-CR₂₀—C(O)—NH(C₁–C₈)alkyl, (C₁–C₈)alkyl-CR₂₀—C(O)—NH₂,-   wherein-   R₂₀ is hydrogen or (C₁–C₈)alkyl.

Particularly preferred is when X is selected from the group consistingof

-   —CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅–C₆cycloalkyl)₂CCN,    (CH₃)₂CCN,

-    —CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁–C₄alkyl)CR₂₀—C(O)-phenyl, (C_(1–C)    ₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkyl,    (C₁–C₄)alkyl-CR₂₀—C(O)—N-di(C₁–C₄)alkyl,    (C₁–C₄)alkyl-CR₂₀—C(O)—NH(C₁–C₄)alkyl, (C₁–C₄)alkyl-CR₂₀—C(O)—NH₂,-   wherein-   R₂₀ is hydrogen or (C₁–C₄)alkyl.

The most preferred substituent is CH₃—CH-phenyl.

In a particularly preferred embodiment of the invention at least one ofG₁, G₂, G₃ and G₄ is ethyl and the others are methyl and G₅ and G₆ areeach independently of the other hydrogen or methyl.

Preferably Y is O.

A preferred group of compounds is, wherein G₁ and G₃ are methyl and G₂and G₄ are ethyl, or G₁ and G₂ are methyl and G₃ and G₄ are ethyl;

-   G₅ and G₆ are each independently of the other hydrogen or methyl;    and-   Y is O;-   n is 1-   R₁ is H, straight or branched C₁–C₁₈alkyl or C₃–C₁₈alkenyl;-   C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;-   phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or    substituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy; or-   —C(O)—C₁–C₃₆alkyl, or an acyl moiety of α,β-unsaturated carboxylic    acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid    having 7 to 15 carbon atoms; and;-   X is selected from the group consisting of —CH₂-phenyl,    CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅–C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

-    —CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁–C₄alkyl)CR₂₀—C(O)-phenyl,    (C₁–C₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkyl,    (C₁–C₄)alkyl-CR₂₀—C(O)—N-di(C₁–C₄)alkyl,    (C₁–C₄)alkyl-CR₂₀—C(O)—NH(C₁–C₄)alkyl, (C₁–C₄)alkyl-CR₂₀—C(O)—NH₂,    wherein-   R₂₀ is hydrogen or (C₁–C₄)alkyl.

Preferred individual compounds are:

Particularly preferred are

-   a) 2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one    oxime (compound 101, Table 1),-   b)    2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-acetoximino-piperidine    (compound 102, Table 1),-   c) 2,2-Diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one    oxime (compound 104, Table 1),-   d)    2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-pivaloyloximino-piperidine    (compound 105, Table 1) or-   e)    2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-benzoyloximino-piperidine    (comjpound 106, Table 1).

A further subject of the invention is a polymerizable composition,comprising

-   a) at least one ethylenically unsaturated monomer or oligomer, and-   b) a compound according to formula (I)

-   G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂ together    and G₃and G₄ together, or G₁ and G₂ together or G₃ and G₄ together    are pentamethylene;-   G₅ and G₆ are each independently of the other hydrogen or    C₁–C₄alkyl; and-   X represents a group such that the free radical X. derived from X is    capable of initiating polymerization of ethylenically unsaturated    monomers;-   n is 1, 2, 3, or 4-   Y is O NR₂ or when n is 1 and R₁ represents alkyl or aryl Y is    additionally a direct bond;-   R₂ is H, C₁–C₁₈alkyl or phenyl;-   if n is 1-   R₁ is H, straight or branched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or    C₃–C₁₈alkinyl, which may be unsubstituted or substitued, by one or    more OH, C₁–C₈alkoxy, carboxy, C₁–C₈alkoxycarbonyl;-   C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;-   phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or    substituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy,    carboxy, C₁–C₈alkoxycarbonyl;-   —C(O)—C₁–C₃₆alkyl, or an acyl moiety of α,β-unsaturated carboxylic    acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid    having 7 to 15 carbon atoms;-   —SO₃ ⁻Q⁺, —PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂,    COOR₂, or Si(Me)₃, wherein Q⁺ is H⁺, ammnonium or an alkali metal    cation;-   if n is 2-   R₁ is C₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which    may be unsubstituted or substitued, by one or more OH, C₁–C₈alkoxy,    carboxy, C₁–C₈alkoxycarbonyl;-   or xylylene; or-   R₁ is a bisacyl radical of an aliphatic dicarboxylic acid having 2    to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic    acid having 8–14 carbon atoms;-   if n is3,-   R₁ is a trivalent radical of an aliphatic, cycloaliphatic or    aromatic tricarboxylic acid; and-   if n is 4, R₁ is a tetravalent radical of an aliphatic,    cycloaliphatic or aromatic tetracarboxylic acid.

Definitions and preferences for the individual substituents have alreadybeen given they apply also for the composition.

Preferably the initiator/regulator compound of formula (I) is present inan amount of from 0.01 mol-% to 20 mol-% more preferably in an amount offrom 0.01 mol-% to 10 mol-% and most preferred in an amount of from 0.05mol-% to 10 mol-% based on the monomer or monomer mixture.

When monomer mixtures are used mol-% is calculated on the averagemolecular weight of the mixture.

Preferably the ethylenically unsaturated monomer or oligomer is selectedfrom the group consisting of ethylene, propylene, n-butylene,i-butylene, styrene, substituted styrene, conjugated dienes, acrolein,vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (meth)acrylonitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides.

Particularly the ethylenically unsaturated monomers are ethylene,propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene,α-C₅–C₁₈alkene, styrene, α-methyl styrene, p-methyl styrene or acompound of formula CH₂═C(R_(a))—(C=Z)-R_(b), wherein R_(a) is hydrogenor C₁–C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstitutedC₁–C₁₈alkoxy, C₂–C₁₀₀alkoxy interrupted by at least one N and/or O atom,or hydroxy-substituted C₁–C₁₈alkoxy, unsubstituted C₁–C₁₈alkylamino,di(C₁–C₁₈alkyl)amino, hydroxy-substituted C₁–C₁₈alkylamino orhydroxy-substituted di(C₁–C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻;

-   An⁻ is a anion of a monovalent organic or inorganic acid;-   Me is a monovalent metal atom or the ammonium ion.-   Z is oxygen or sulfur.

Examples for R_(a) as C₂–C₁₀₀alkoxy interrupted by at least one O atomare of formula

-    wherein R_(c) is C₁–C₂₅alkyl, phenyl or phenyl substituted by    C₁–C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1    to 50. These monomers are for example derived from non ionic    surfactants by acrylation of the corresponding alkoxylated alcohols    or phenols. The repeating units may be derived from ethylene oxide,    propylene oxide or mixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

-    An⁻, wherein An⁻ and R_(a) have the meaning as defined above and    R_(e) is methyl or benzyl. An is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

Further acrylate monomers are

-   Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁–C₄alkoxy, unsubstitutedC₁–C₄alkylamino, di(C₁–C₄alkyl)amino, hydroxy-substitutedC₁–C₄alkylamino or hydroxy-substituted di(C₁–C₄alkyl)amino;and Z isoxygen.

Particularly preferred ethylenically unsaturated monomers are styrene,methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert.butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

A further subject of the invention is a process for preparing anoligomer, a cooligomer, a polymer or a copolymer (block or random) byfree radical polymerization of at least one ethylenically unsaturatedmonomer or oligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of an initiator compound of formula(I) under reaction conditions capable of effecting scission of the O—Cbond to form two free radicals, the radical .X being capable ofinitiating polymerization.

Preferred is a process wherein the scission of the O—C bond is effectedby ultrasonic treatment, heating or exposure to electromagneticradiation, ranging from γ to microwaves.

More preferably the scission of the O—C bond is effected by heating andtakes place at a temperature of between 50° C. and 160° C.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

Preferred processes use as little solvents as possible. In the reactionmixture it is preferred to use more than 30% by weight of monomer andinitiator, particularly preferably more than 50% and most preferrablymore than 80%.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons(chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethyleneglycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexylacetate) and ethers (diethyl ether, dibutyl ether, ethylene glycoldimethyl ether), or mixtures thereof.

The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

The process is particularly useful for the preparation of blockcopolymers.

Block copolymers are, for example, block copolymers of polystyrene andpolyacrylate (e.g., poly(styrene-co-acrylate) orpoly(styrene-co-acrylate-co-styrene). They are usefull as adhesives oras compatibilizers for polymer blends or as polymer toughening agents.poly(methylmethacrylate-co-acrylate) diblock copolymers orpoly(methylacrylate-co-acrylateco-methacrylate) triblock copolymers) areuseful as dispersing agents for coating systeme, as coating additives(e.g. rheological agents, compatibilizers, reactive diluents) or asresin component in coatings(e.g. high solid paints) Block copolymers ofstyrene, (meth)acrylates and/or acrylonitrile are useful for plastics,elastomers and adhesives.

Furthermore, block copolymers of this invention, wherein the blocksalternate between polar monomers and non-polar monomers, are useful inmany applications as amphiphilic surfactants or dispersants forpreparing highly uniform polymer blends. The (co)polymers of the presentinvention may have a number average molecular weight from 1 000 to 400000 g/mol, preferably from 2 000 to 250 000 g/mol and, more preferably,from 2 000 to 200 000 g/mol. When produced in bulk, the number averagemolecular weight may be up to 500 000 (with the same minimum weights asmentioned above). The number average molecular weight may be determinedby size exclusion chromatography (SEC), gel permeation chromatography(GPC), matrix assisted laser desorptionrionization mass spectrometry(MALDI-MS) or, if the initiator carries a group which can be easilydistinguished from the monomer(s), by NMR spectroscopy or otherconventional methods.

The polymers or copolymers of the present invention have preferably apolydispersity of from 1.0 to 2, more preferably of from 1.1 to 1.9 andmost preferably from 1.1 to 1.8.

Thus, the present invention also encompasses in the synthesis novelblock, multi-block, star, gradient, random, hyperbranched and dendriticcopolymers, as well as graft or copolymers.

The polymers prepared by the present invention are useful for followingapplications:

adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers,adhesion promoters, corrosion inhibitors, viscosity improvers,lubricants, rheology modifiers, thickeners, crosslinkers, papertreatment, water treatment, electronic materials, paints, coatings,photography, ink materials, imaging materials, superabsorbants,cosmetics, hair products, preservatives, biocide materials or modifiersfor asphalt, leather, textiles, ceramics and wood.

Because the present polymerizaton is a “living” polymerization, it canbe started and stopped practically at will. Furthermore, the polymerproduct retains the functional alkoxyamine group allowing a continuationof the polymerization in a living matter. Thus, in one embodiment ofthis invention, once the first monomer is consumed in the initialpolymerizing step a second monomer can then be added to form a secondblock on the growing polymer chain in a second polymerization step.Therefore it is possible to carry out additional polymerizations withthe same or different monomer(s) to prepare multi-block copolymers.

Furthermore, since this is a radical polymerization, blocks can beprepared in essentially any order. One is not necessarily restricted topreparing block copolymers where the sequential polymerizing steps mustflow from the least stabilized polymer intermediate to the moststabilized polymer intermediate, such as is the case in ionicpolymerization. Thus it is possible to prepare a multi-block copolymerin which a polyacrylonitrile or a poly(meth)acrylate block is preparedfirst, then a styrene or butadiene block is attached thereto, and so on.

Furthermore, there is no linking group required for joining thedifferent blocks of the present block copolymer. One can simply addsuccessive monomers to form successive blocks.

A plurality of specifically designed polymers and copolymers areaccessible by the present invention, such as star and graft (co)polymersas described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107,pages 1623–1627, dendrimers as described by K. Matyaszewski et al. inMacrmolecules 1996, Vol 29, No. 12, pages 4167–4171, graft (co)polymersas described by C. J. Hawker et al. in Macromol. Chem. Phys. 198,155–166(1997), random copolymers as described by C. J. Hawker inMacromolecules 1996, 29, 2686–2688, or diblock and triblock copolymersas described by N. A. Listigovers in Macromolecules 1996, 29, 8992–8993.

Also subject of the invention is a compound of formula (II)

wherein

-   G₁ and G₃ are independently C₁–C₄alkyl;-   G₂ and G₄ are independently C₂–C₄alkyl;-   G₅ and G₆ are each independently of the other hydrogen or    C₁–C₄alkyl;-   n is 1, 2, 3, or 4-   Y is O, NR₂ or when n is 1 and R₁ represents alkyl or aryl Y is    additionally a direct bond;-   R₂ is H, C₁–C₁₈alkyl or phenyl;-   if n is 1-   R₁ is H, straight or branched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or    C₃–C₁₈alkinyl, which may be unsubstituted or substitued, by one or    more OH, C₁–C₈alkoxy, carboxy, C₁–C₈alkoxycarbonyl;-   C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;-   phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or    substituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy,    carboxy, C₁–C₈alkoxycarbonyl;-   —C(O)—C₁–C₃₆alkyl, or an acyl moiety of a α,β-unsaturated carboxylic    acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid    having 7 to 15 carbon atoms;-   —SO₃ ⁻Q⁺, —PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂,    COOR₂, or Si(Me)₃, wherein Q⁺ is H⁺, ammnonium or an alkali metal    cation;-   if n is 2-   R₁ is C₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which    may be unsubstituted or substitued, by one or more OH, C₁–C₈alkoxy,    carboxy, C₁–C₈alkoxycarbonyl;-   or xylylene; or-   R₁ is a bisacyl radical of an aliphatic dicarboxylic acid having 2    to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic    acid having 8–14 carbon atoms;-   if n is 3,-   R₁ is a trivalent radical of an aliphatic, cycloaliphatic or    aromatic tricarboxylic acid; and-   if n is 4, R₁ is a tetravalent radical of an aliphatic,    cycloaliphatic or aromatic tetracarboxylic acid.

Definitions and preferences for the individual substituents have alreadybeen given and apply also for the compounds of formula (II).

Consequently a further subject of the invention is a polymerizablecomposition, comprising

-   a) at least one ethylenically unsaturated monomer or oligomer, and-   b) a compound according to formula (II)

-   G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂ together    and G₃ and G₄ together, or G₁ and G₂ together or G₃ and G₄ together    are pentamethylene;-   G₅ and G₆ are each independently of the other hydrogen or    C₁–C₄alkyl;-   n is 1, 2, 3, or 4-   Y is O, NR₂ or when n is 1 and R₁ represents alkyl or aryl Y is    additionally a direct bond;-   R₂ is H, C₁–C₁₈alkyl or phenyl;-   if n is 1-   R₁ is H, straight or branched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or    C₃–C₁₈alkinyl, which may be unsubstituted or substitued, by one or    more OH, C₁–C₈alkoxy, carboxy, C₁–C₈alkoxycarbonyl;-   C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;-   phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or    substituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy,    carboxy, C₁–C₈alkoxycarbonyl;-   —C(O)—C₁–C₃₆alkyl, or an acyl moiety of a α,β-unsaturated carboxylic    acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid    having 7 to 15 carbon atoms;-   —SO₃ ⁻Q⁺, —PO(O⁻Q⁺)₂, —P(O)(OR₂)₂, —SO₂—R₂, —CO—NH—R₂, —CONH₂,    COOR₂, or Si(Me)₃, wherein Q⁺ is H⁺, ammnonium or an alkali metal    cation;-   if n is 2-   R₁ is C₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which    may be unsubstituted or substitued, by one or more OH, C₁–C₈alkoxy,    carboxy, C₁–C₈alkoxycarbonyl;-   or xylylene; or-   R₁ is a bisacyl radical of an aliphatic dicarboxylic acid having 2    to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic    acid having 8–14 carbon atoms;-   if n is 3,-   R₁ is a trivalent radical of an aliphatic, cycloaliphatic or    aromatic tricarboxylic acid; and-   if n is 4, R₁ is a tetravalent radical of an aliphatic,    cycloaliphatic or aromatic tetracarboxylic acid; and-   c) a source of free radicals.

The source of radicals may be a bis-azo compound, a peroxide, a peresteror a hydroperoxide.

The production of C-centered radicals is described, inter alia, inHouben Weyl, Methoden der Organischen Chemie, Vol. E 19a, pages 60–147.These methods can be applied in general analogy.

Preferably, the source of radicals is 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide.

Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonylperoxide, diisopropyl peroxy dicarbonate, t-amyl pemeodecanoate, t-butylpemeodecanoate, t-butyl perpivalate, t-amylperpivalate,bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl)peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoylperoxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide,t-butyl perisobutyrate, t-butyl permaleinate,1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t-butylperoxy) butane, 2,2 bis(t-butylperoxy)propane, dicumyl peroxide,2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)-3,5-dimethyl 1,2-dioxolane,di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

These compounds are commercially available.

If more than one radical source is used, a mixture of substitutionpatterns is obtainable.

Preferably the compound of formula (II) is present in an amount of from0.01 mol-% to 20 mol-% , based on the monomer or monomer mixture, morepreferably of from 0.01 mol-% to 10 mol-% and most preferably of from0.05 mol-% to 10 mol-%.

The radical source is preferably present in an amount of from 0.01 mol-%to 20 mol-%, more preferred in an amount of from 0.01 mol-% to 10 mol-%and most preferred in an amount of from 0.05 mol-% to 10 mol-% based onthe monomer or monomer mixture.

The molar ratio of the radical source to the compound of formula II maybe from 1:10 to 10:1, preferably from 1:5 to 5:1 and more preferablyfrom 1:2 to 2:1.

Also subject of the invention is a process for preparing an oligomer, acooligomer, a polymer or a copolymer (block or random) by free radicalpolymerization of at least one ethylenically unsaturated monomer oroligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of a compound of formula (II) and asource of free radicals the radical being capable of initiatingpolymerization.

Definitions and preferences as well as reaction conditions have alreadybeen given and apply also for the process.

Yet further subjects of the invention are a polymer prepared by radicalpolymerization according to one of the above mentioned processes havingattached a group of formula (III)

wherein the substituents are as defined above; and the use of a compoundof formula (I) or of a compound of formula (II) together with a sourceof free radicals for the controlled radical (co)polymerization ofethylenically unsaturated monomers.

The compounds of formula II can be prepared for example according to E.G. Rozantsev, A. V. Chudinov, V. D. Sholle.: Izv. Akad. Nauk. SSSR, Ser.Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxidein a condensation reaction with hydroxylamine and subsequent reaction ofthe OH group.

Another possible reaction scheme is to first react the 4-oxonitroxidewith an amine or hydrazine to yield the corresponding imine as forexample described in FR 1503149.

It is, however also possible to firstly react the 4-oxopiperidine withhydroxylamine, hydrazine or with a semicarbacide to the correspondingimino-compound and oxidising the imino piperidine to the correspondingnitroxide.

The alkoxyamines of formula I may be prepared from the correspondingnitroxides as for example described in GB 2335190.

A particularly suitable process for the preparation of the compounds offormula (I) starts from the 4-oxo-alkoxyamines, the preparation of whichis also described in GB 2335190:

Since the 4-oxo-alkoxyamines already may have several asymmetricalcarbon atoms, a variety of stereo isomers is usually obtained as mixturewith different ratios of the individual isomers. It is however possibleto separate the individual isomers in pure form. Mixtures of the stereoisomers as well as the pure individual isomers are within the scope ofthe present invention.

The ratio of the stereo isomers can be influenced by suitable catalystssuch as bases or acids. This isomer equilibration can be done at thestage of the 4-oxo-alkoxyamine, during the imine forming reaction or atthe stage of the final 4-imino-alkoxyamine. The shifting of the stereoisomer ratio allows to increase the overall yield, achievable forexample by crystallisation.

Suitable bases are for example alkali metal or alkaline earth metalhydroxides or alcoholates such as LiOH, KOH, NaOH or Ca(OH)₂, NaOCH₃,NaOCH₂CH₃, Mg-ethanolate or K-tert. butylate. Also suitable bases areamines, particularly secondary or tertiary amines, such as piperidine,morpholine, pyridine, triethylamine or amidines such as DBU(diazabicycloundecane), DABCO (diazabicyclooctane).

Suitable acids are for example strong mineral acids, such as HCl, H₂SO₄,H₃po₄ organic sulfonic acids, such as CH₃SO₃H or para-toluene sulfonicacid, trichloro acetic acid or trifluoro acetic acid, organic acids,such as formic acid, acetic acid or benzoic acid, Lewis acids, such asAlCl₃ or BF₃, complex acids, such as HBF₄ or HPF₆.

A further aspect of the instant invention is an improved process for thepreparation of a compound of formula (I)

(I) comprising reacting a compound of formula (X)

(X) with a compound of formula (XI) R₁—Y—NH₂ (XI) wherein thesubstituents have the meaning as defined above, characterized in thatthe compound of formula (X) is firstly treated with an acid or basecatalyst or the acid or base catalyst is added during the imine formingreaction.

The imine forming reaction from a ketone and a substituted amine isknown per se.

Suitable acid or base catalysts have already been mentioned. They arepreferably used in a concentration of from 0.01 to 10%, more preferablyof from 0.1 to 10% and most preferably of from 1 to 5% by weight basedon the educt.

If the compound of formula (X) is pretreated with the catalyst thetreatment duration is typically of from 1 minute to 10 hours, morepreferably from 10 minutes to two hours.

The treatment may be preferably done at room temperature, however, it isalso possible to work at 0° C. up to 150° C.

It can be done in solution or in bulk. Typical solvents are alcohols,ethers, esters, ketones aliphatic or aromatic hydrocarbons.

The pretreated compound of formula (X) can be subjected to the imineforming reaction immediately or after storage. The catalyst can beremoved or left in the reaction mixture.

When the acid or base catalyst is added during the reaction, it ispreferably added at the beginning. It is, however, possible to add thecatalyst at a later stage.

The following examples illustrate the invention.

A) PREPARATION EXAMPLES Example A12,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oxime(Table 1, Comp. 101)

2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-oxopiperidine preparedaccording to DE 199 09 767 A1 is dissolved in methanol containing 10% byweight of KOH and stirred for 5 hours at room temperature. Methanol isevaporated, the residue is washed with water and dried in vacuo. Asolution of 95.24 g (0.3 mol) of2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-oxopiperidine and 29.7g (0.45 mol) 50% aqueous hydroxylamine solution in 150 ml of methanol isstirred under reflux during 5 h. The suspension is then cooled to −8° C.and filtered. The solid is washed with 100 ml of a cold (−20° C.)methanol and dried to afford 64 g (64.1%) of the title compound as awhite, microcrystalline powder, mp 130–145° C. C₂₀H₃₂N₂O₂ (332.49)calculated C, 72.25%; H, 9.70%; N, 8.43%. found 72.19% C; 9.54% H; 8.43% N.

Example A22,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-acetoximino-piperidine(Table 1, Comp. 102)

To a suspension of 10 g (0.03 mol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)piperidine-4-one oxime in20 ml ethylacetate are added 0.1 g 4-dimethylamino-pyridin and 3.8 ml(0.04 mol) acetanhydride. The mixture is then stirred 2 h at roomtemperature. The homogeneous clear solution formed during this period iswashed with water and NaHCO₃ solution and evaporated under vacuo toafford 11.2 g (99.7%) of the title compound as a colorless oil.

¹H-NMR (300 HMz, CDCl₃): 7.33–7.20 m (5ArH), 4.81–4.72 m (1H), 3.3–0.62m (22H), 2.15 s (OC—CH₃), 1.45 d (CH₃).

Example A32,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-onesemicarbazone (Table 1, Comp. 103)

2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-oxopiperidine preparedaccording to DE 199 09 767 A1 is dissolved in methanol containing 10% byweight of KOH and stirred for 5 hours at room temperature. Methanol isevaporated, the residue is washed with water and dried in vacuo. To asolution of 6.4 g (0.02 mol)2,6-diethyl-2,3,6-trimethyl-1-(1-pheyl-ethoxy)-piperidine-4-one in 20 mlmethanol are added 3.3 g (0.03 mol) semicarbazide hydrochloride and 1.67g (0.025 mol) KOH (85%). The mixture is stirred under reflux 5 h andthen diluted with 200 ml water. The precipitate is extracted into 100 mlof dichloromethane, the organic layer is washed with water, dryied overMgSO4 and evaporated to give 7.8 g (98.8%) of the title compound as aslightly yellow resin.

¹H-NMR (300 HMz, CDCl₃): 8.5–7.7 bm (1H), 7.39–7.16 m (5 ArH), 6.5–5.0bm (2H), 4.87–4.64 m (1 H), 2.7–0.63 m (25H)

Example A42,2-Diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperidineone-4-one oxime(Table 1, Comp. 104)

2,2-diethyl-6,6-dimethyl-piperidine-4-one (preparation see Monatsheftefür Chemie 88, 464 (1957)) is converted into the corresponding nitroxidewhich is further transformed into2,2-diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one using themethodology described in DE 199 09 767 A1. Colorless oil, ¹H-NMR (300HMz, CDCl₃): 7.34–7.23 m (5 ArH), 4.80–4.73 m (1H), 2.6–0.64 m (20H),1.49 d (CH₃). This alkoxyamine (6.06 g, 0.02 mol) is then, in analogy toexample 1, reacted with 1.77 ml (0.03 mol) of 50% aqueous hydroxylaminein 10 ml methanol. The title compound (5.15 g, 81%) is obtained afterchromatography on silica gel with hexane-ethylacetate (4:1) as acolorless oil.

¹H-NMR (300 HMz, CDCl₃): 8.5 bs (1H), 7.36–7.21 m (5ArH), 4.78–4.70 m(1H), 3.1–0.64 m (20H), 1.52 d (CH₃).

Example A52,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-pivaloyloximino-piperidine(Table 1, Comp. 105)

To a suspension of 10 g (0.03 mol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oximein 70 ml toluene are added 4.6 ml (0.033 mol) triethylamine andtherafter dropwise 4 g (0.033 mol) pivaloylchlorid. The mixture is thenstirred 17 h at rt. The precipitated Et₃N.HCl is filtered off, thefiltrate is washed with 2×50 ml 5% NaOH, dried over MgSO₄ and evaporatedin vacuo. The residue is chromatographed on silica gel withhexane-ethylacetate (9:1) to afford 12.1 g (96.8%) of the title compoundas a colorless oil.

¹H-NMR (300 HMz, CDCl₃): 7.34–7.20 m (5ArH), 4.81–4.73 m (1H), 3.3–0.62m (22H), 1.45 d (CH₃), 1.30 bs (9H, t-Bu).

Example A62,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-benzoyloximino-pineridine(Table 1, Comp. 106)

From 10 g (0.03 mol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oxime,4.65 g (0.033 mol) benzoylchloride and 4.6 ml (0.033 mol) triethylamineare prepared in analogy to example A5. 8.1 g (61.8%) of the titlecompound is obtained as a colorless solid after treating with methanol,mp. 78–125° C. (mixture of isomers).

¹H-NMR (300 HMz, CDCl₃): 8.05–8.0 (m, 2ArH), 7.59–7.54 m (1ArH),7.50–7.42 m (2ArH), 7.31–6.91 m (5ArH), 4.83–4.75 m (1H), 3.3–0.62 m(22H), 1.47 d (CH₃).

Example A72,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-N-ethylcarbamoyl-oximino-piperidine(Table 1, Comp. 107)

To a suspension of 10 g (0.03 mol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oximein 50 ml toluene are added 2.6 ml (0.033 mol) ethylisocyanate. Themixture is stirred 3 h at rt and thereafter heated for another 3 h at35° C., then filtered and evaporated under reduced pressure to afford12.1 g (99.2%) of the title compound as a colorless oil.

¹H-NMR (300 HMz, CDCl₃): 7.33–7.12 m (5ArH), 6.36–6.30 bs (NH),4.80–4.71 m (1H), 3.39–3.30 (q, CH₂), 3.25–0.62 m (25H), 1.45 d (CH₃).

Example A82,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-stearoyloximino-piperidine(Table 1, Comp. 108)

10 g (0.03 mol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oxime,9.7 9 (0.032 mol) stearoylchloride and 4.6 ml (0.033 mol) triethylamineare reacted in analogy to example A5. 16.65 g (92.7%) of the titlecompound is obtained as a colorless oil after chromatography on silicagel with hexane-ethylacetate (10:1).

¹H-NMR (300 HMz, CDCl₃): 7.33–7.20 m (5ArH), 4.78–4.74 m (1H), 3.20–0.62m (57H), 1.45 d (CH₃).

Example A92,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-methoximino-piperidine(Table 1, Comp. 109)

To a suspension of 12 g (0.036 mol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oximein 40 ml dimethylformamide is added under nitrogen 1.75 g (0.0397 mol)sodium hydride (55% in mineral oil) and the mixture is stirred at 35° C.for 2 h. To the slightly turbid, yellow solution is then dropwise addedat 10–20° C. 5.65 g (0.0397 mol) methyl iodide. The mixture is dilutedafter 18 h stirring at room temperature with 200 ml cold water andextracted with 2×100 ml hexane. The extracts are dried over MgSO4 andevaporated under reduced pressure. Chromatography of the residue onsilica gel with hexane-ethyl acetate (24:1) afforded 9.6 g (77%) of thetitle compound as a colorless oil.

¹H-NMR (300 HMz, CDCl₃): 7.32–7.19 m (5ArH), 4.80–4.72 m (1H), 3.82 (s,CH₃O), 3.25–0.62 m (22H), 1.45 d (CH₃).

Example A101-Benzyloxy-2,6-diethyl-2,3,6-trimethyl-piperidine-4-one-O-benzyloxime(Table 1, Comp. 110)

a) A solution of 20 g (96.8 mmol)2,6-diethyl-2,3,6-trimethyl-piperidine-4-one oxime-1-oxyl in 200 mlpetroleum ether (40–60° C.) was under nitrogen 17 h vigorously stirredwith a solution of 80 g of sodium ascorbate in 100 ml water. The slurrywas cooled to 10° C., filtered, the precipitate was washed with waterand hexane and dried in vacuo to give 19.95 g of a white2,6-diethyl-2,3,6-trimethyl-1-hydroxy-piperidineone-4-one.

b) To a slurry of 3.8 g (87.5 mmol) sodium hydride (55% in mineral oil)in 40 ml DMFA were added 8 g (35 mmol)2,6-diethyl-2,3,6-trimethyl-1-hydroxy-piperidine-4one. The mixture wasstirred for 1 h at 30° C. and then cooled to 5° C. Thereafter, 10.4 ml(87.5 mmol) benzyl bromide were added dropwise at 5–10° C. The mixturewas stirred for additional 3 h, then poured into 200 ml of cold waterand extracted with 2×50 ml methyl-t-butyl ether. The extracts wereevaporated and chromatographed on silica gel with hexane-ethylacetate(39:1) to give 10.8 g (75.5%) of the title compound as a colorles oil.

¹H-NMR (300 MHz, CDCl₃): 7.5–7.2 m (10 ArH), 5.1–5.04 m (2H), 4.9–4.7 m(2 H), 3.4–0.7 (m, 22H).

Example A111-Allyloxy-2,6-diethyl-2,3,6-trimethyl-piperidine-4-one-O-allyl-oxime(Table 1, Comp. 111)

To a slurry of 5.2 g (120 mmol) sodium hydride (55% in mineral oil) in50 ml DMFA were added 9.6 g (42 mmol)2,6-diethyl-2,3,6-trimethyl-1-hydroxy-piperidine-4-one. The mixture wasstirred for 75 minutes at 30° C. and then cooled to room temperature.Thereafter, 14.5 g (120 mmol) allyl bromide were added dropwise at roomtemperature. The mixture was stirred for additional 2 h, then pouredinto 200 ml of cold water and extracted with 3×50 ml hexane. Theextracts were evaporated and chromatographed on silica gel withhexane-ethylacetate (39:1) to give 10.75 g (83%) of the title compoundas a colorles oil.

For C₁₈H₃₂N₂O₂ calculated: C, 70.09%; H, 10.46%; N, 9.08%. found C,70.03; H, 11.23%; N, 9.14%.

Example A122,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one-O-diethylphosphonato-oxime(Table 1, Comp. 112)

To a stirred suspension of 10 g (30 mmol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oximein 70 ml toluene are added 4.6 ml (33 mmol) of triethylamine, 5.7 ml (33mmol) of diethylchlorophosphate and 0.15 g of 4-dimethylaminopyridine.The mixture is stirred for 72 h at room temperature, and heatedtherafter for additional 24 h at 60° C. It is then cooled to roomtemperature, washed 2× with 50 ml water, dried over MgSO₄ andevaporated. The residue is chromatographed on silica gel withhexane-ethyl acetate (2:1) to give 9.3 g (66%) of the title compound asa colorless oil.

¹H-NMR (300 MHz, CDCl₃): 7.33–7.22 m(5H), 4.79–4.74 m (1H), 4.26–4.16m(4H), 3.5–0.5 m (31H). ³¹p-NMR (162 MHz, CDCl₃): 1.655–1.355 m

Example A13[2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-ylideneaminooxy]-aceticacid-teroom temperature.-butyl ester (Table 1, Comp. 113)

To a suspension of 16.62 g (50 mmol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oximein 70 ml dry DMFA were added 2.4 g (55 mmol) sodium hydride (55% inmineral oil). The mixture was stirred at 40° C. for 1 hour and cooled to10° C. Thereafter, 8.1 ml (55 mmol) of t-butyl-bromoacetate were addeddropwise and the mixture was stirred at room temperature for 18 hours.It was then diluted with 300 ml water and extracted twice with 100 ml ofmethyl-t-butyl ether. The extracts were washed 3 times with 50 ml water,dried over MgSO₄ and evaporated. The residue was chromatographed onsilica gel with hexane-ethyl acetate (19:1) to give 20.85 g (93.5%) ofthe title compound as a colorless oil.

¹H-NMR (300 MHz, CDCl₃): 7.33–7.19 m (5 H), 4.81–4.73 m (1H), 4.47–4.45m (2H), 3.1–0.5 m (25 H), 1.46 s (9H)

Example A14[2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-ylideneaminooxy]-aceticacid (Table 1, Comp. 114)

In 30 ml of trifluoroacetic acid were dissolved 10.1 g (22.6 mmol) of[2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-ylideneaminooxy]-aceticacid-teroom temperature.-butyl ester and the clear solution was stirredunder nitrogen at room temperature for 4 hours. The mixture was thendiluted with 300 ml water and extracted with 2×50 ml of methyl-t-butylether. The extracts were washed 3 times with 50 ml water, evaporated andchromatographed on silica gel with hexane-ethylacetate 2:1 to give 4.7 g(53%) of the title compound as a colorless oil.

¹H-NMR (300 MHz, CDCl₃): 7.37–7.20 m (5 H), 4.80–4.72 m (1 H), 4.62–4.60m (2H), 3.4–0.5 m (26H).

Example A15 2,2,6,6-Tetramethyl-1-(1-phenyl-ethoxy)-piperidine-4-oneoxime (Table 1, Comp. 115)

To a solution of 36 g (130 mmol) of2,2,6,6-tetramethyl-1-(1-phenyl-ethoxy)-piperidine-4-one (prepared asdescribed in Eur. Pat. Appl. (1990), E

389430 A1) in 50 ml of methanol were added 26 g (390 mmol) of 50%aqueous hydroxylamine. The mixture was refluxed for 90 minutes and thenevaporated. The residue was chromatographed on 450 g of silica gel withhexane-ethyl acetate (4:1) to give 21.05 g (55%) of the title compoundas a colorless oil, slowly solidifying on standing.

¹H-NMR (300 MHz, CDCl₃): 8.9 bs 1H, 7.37–7.05 m (5 H), 4.83 q (1 H),3.2–0.7 m (16H), 1.51 d (3H).

Example A162,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-oneoxime-adipic acid ester (Table 1, Comp. 116)

To a stirred suspension of 10.5 g (31.5 mmol)2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oximein 70 ml toluene are added 4.5 ml (32.5 mmol) of triethylamine and 2.75g (15 mmol) of adipic acid dichloride. The mixture is stirred for 22 hat room temperature, washed 2× with 50 ml water, dried over MgSO₄ andevaporated. The residue is chromatographed on silica gel withhexane-ethyl acetate (5:1) to give 9.35 g (76%) of the title compound asa colorless oil.

¹H-NMR (300 MHz, CDCl₃): 7.33–7.20 m (10 H), 4.8–4.74 m (2 H), 3.4–0.5 m(58 H)

Example A17 2,6-Diethyl-2,3,6-trimethyl-peridine-4-one oxime-1-oxyl(Table 1, Comp. 117)

In a solution of 4.2 g (20 mmol)2,6-diethyl-2,3,6-trimethyl-piperidine-4-one oxime (prepared asdescribed by Brunetti, Heimo; Rody, Jean; Sama, Nobuo; Kurumada,Tomoyuki.: Ger. Offen. (1976), DE 2621924) in 20 ml ethylacetate wasadded dropwise under stirring at room temperature the solution of 7.4 g(30 mmol) of m-chlorperbenzoic acid (70%) in 20 ml of ethyl acetate. Themixture after completed addition is stirred for additional 80 minutes atroom temperature, diluted with 100 ml hexane, washed 3× with 1M NaHCO₃,dried over MgSO₄ and evaporated to give 4.5 g (˜100%) of a thick red oilwhich solidifies upon standing.

Example A18 2,6-Diethyl-2,3,6-trimethyl-piperidine-4-acetoximino-1-oxyl(Table 1, Comp. 118)

-   a) To a solution of 45.3 g (0.213 mol) of    2,6-diethyl-2,3,6-trimethyl-piperidine-4-one oxime in 40 ml toluene    were added 0.2 g 4-dimethylaminopyridin and 20.8 ml acetic    anhydride. The mixture was stirred for 75 minutes at 30° C., then    diluted with 100 ml toluene, washed with 50 ml 30% NaOH and 50 ml    water. The organic layer was dried over MgSO₄ and evaporated to give    46.65 g 2,6-diethyl-2,3,6-trimethyl-4-acetoximino-piperidine.

b) To a solution of 25.45 g (0.1 mol)2,6-Diethyl-2,3,6trimethyl-4-acetoximino-piperidine in 100 mlethylacetate were under stirring at room temperature added 29.9 ml (0.19mol) peracetic acid (40% in acetic acid). The mixture for stirred for 22h at room temperature, diluted with 100 ml hexane, washed with 100 mlwater and 100 ml 1 M NaHCO₃, dried over MgSO₄ and evaporated. Theresidue was chromatographed on silica gel with hexane-ethylacetate (4:1)to give 12.45 g (46%) of the title compound as a red oil.

For C₁₂H₁₃N₂O₂ (227.33) calculated: C, 62.43%; H, 9.35%; N, 10.40%.found 62.46%, H; 9.24%, N; 10.28%.

Example A192,6-Diethyl-2,3,6-trimethyl-piperidine-4-one-O-benzyl-oxime-1-oxyl(Table 1, Comp. 119)

A mixture of 25 ml dichloromethane, 26 g of 50% aqueous NaOH, 17.3 ml(0.15 mol) benzyl chloride, 0.66 g (C₄H₉)₄NHSO₄ and 22.7 g (0.1 mmol)2,6-diethyl-2,3,6-trimethyl-piperidine-4-one oxime-1-oxyl is vigorouslystirred 12 hours at room temperature. The organic layer is thenseparated, washed 3× with 20 ml water, dried over MgSO₄ and evaporated,at the end at 0.01 mbar/58° C. to give 31.4 g (99%) of the titlecompound as a red oil.

Example A202,6-Diethyl-2,3,6-trimethyl-piperidine-4-one-O-methyl-oxime-1-oxyl(Table 1, Comp. 120)

A mixture of 30 ml dichloromethane, 50 g of 50% aqueous NaOH, 7 mlmethyl iodide, 0.35 g (C₄H₉)₄NHSO₄ and 1.75 g (7.7 mmol)2,6-diethyl-2,3,6-trimethyl-piperidine-4-one oxime-1-oxyl is vigorouslystirred 5 hours at room temperature. The organic layer is thenseparated, washed 3× with 20 ml water, dried over MgSO₄ and evaporated.The red oily residue is chromatographed on silica gel withhexane-ethylacetate (9:1) to give 1.52 g (82%) of the title compound asa red oil.

The compounds prepared are summarized in table 1.

TABLE 1 Compound No. Structure 101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

B) POLYMERIZATION EXAMPLES

General Remarks:

Solvents and monomers are distilled over a Vigreux column under argonatmosphere or under vacuum, shortly before being used.

To remove oxygen all polymerization reaction mixtures are flushed beforepolymerization with argon and evacuated under vaccum applying afreeze-thaw cycle. The reaction mixtures are then polymerized underargon atmosphere.

At the start of the polymerization reaction, all starting materials arehomogeneously dissolved.

Conversion is determined by removing unreacted monomers from the polymerat 80° C. and 0.002 torr for at least 60minutes, weighing the remainingpolymer and subtract the weight of the initiator.

Characterization of the polymers is carried out by MALDI-MS (MatrixAssisted Laser Desorption Ionization Mass Spectrometry) and/or GPC (Gelpermeation Chromatography).

MALDI-MS: Measurements are performed on a linear TOF (Time Of Flight)MALDI-MS LDI-1700 Linear Scientific Inc., Reno, USA. The matrix is2,5-dihydroxybenzoic acid and the laser wavelength is 337 nm.

GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS. Tetrahydrofurane(THF) is used as a solvent and is pumped at 1 ml/min. Two chromatographycolumns are put in series: type plgel 5 μm mixed-C of POLYMERINSTRUMENTS, Shropshire, UK. Measurements are performed at 40° C. Thecolumns are calibrated with low polydispersity polystyrenes having Mnfrom 200 to 2 000 000 Dalton. Detection is carried out using aRI-Detector ERC-7515A of ERCATECH AG at 30° C.

Example B1 Polymerization of n-butylacrylat with 1.5 mol % of compound101 (Tabel 1) at 145° C.

In a 50 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 1.556 g (4.68 mmol) of compound 101 and 40 g (312mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 5 h. The reaction mixture is then cooled to 70° C. Theremaining monomer is removed by evaporation under high vacuum. 33.9 g(84.8%) of the initial monomer have reacted. A clear orange viscousfluid is obtained.

Mn=7600, Mw=10260, PD=1.35

Example B2 Polymerization of n-butylacrylat with 1.5 mol % of compound102 (Tabel 1) at 145° C.

In a 50 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 1.753 g (4.68 mmol) of compound 102 and 40 g (312mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 5 h. The reaction mixture is then cooled to 70° C. Theremaining monomer is removed by evaporation under high vacuum. 31.6 g(79%) of the initial monomer have reacted. A clear orange viscous fluidis obtained.

Mn=6060, Mw=7575, PD=1.25

Example B3 Polymerization of n-butylacrylat with 1.5 mol % of compound103 (Tabel 1) at 145° C.

In a 50 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 438 mg (1.17 mmol) of compound 103 and 10 g (78 mmol)of n-butylacrylate are mixed and degased. The clear solution obtained isheated under argon to 145° C. and polymerization is carried out during 5h. The reaction mixture is then cooled to 70° C. The remaining monomeris removed by evaporation under high vacuum. 7.7 g (77%) of the initialmonomer have reacted. A clear colourless viscous fluid is obtained.

Mn=9150, Mw=12810, PD=1.4

Example B4 Polymerization of n-butylacrylat with 1.5 mol % of compound104 (Tabel 1) at 145° C.

In a 50 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 373 mg (1.17 mmol) of compound 104 and 10 g (78 mmol)of n-butylacrylate are mixed and degased. The clear solution obtained isheated under argon to 145° C. and polymerization is carried out during 5h. The reaction mixture is then cooled to 70° C. The remaining monomeris removed by evaporation under high vacuum. 6.5 g (65%) of the initialmonomer have reacted. A clear colourless viscous fluid is obtained.

Mn=6380, Mw=9890, PD=1.55

Example B5 Polymerization of styrene with 1 mol % of compound 105(Table 1) at 130° C.

In a 100 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 1.816 g (4.36 mmol) of compound 105 and 45.45 g (436mmol) of styrene are mixed and degased. The clear solution obtained isheated under argon to 130° C. and polymerization is carried out during 6h. The reaction mixture is then cooled to 80° C. The remaining monomeris removed by evaporation under high vacuum to give 40.45 g (89%) of thepolystyrene.

Mn=7844, Mw=9107, PD=1.2

Example B6 Polymerization of styrene with 1 mol % of compound 106(Table 1) at 130° C.

In a 100 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 1.905 g (4.36 mmol) of compound 106 and 45.45 g (436mmol) of styrene are mixed and degased. The clear solution obtained isheated under argon to 130° C. and polymerization is carried out during 6h. The reaction mixture is then cooled to 80° C. The remaining monomeris removed by evaporation under high vacuum to give 43.2 g (96%) of thepolystyrene.

Mn=8400, Mw=9436, PD=1.1

Example B7 Polymerization of styrene with 1 mol % of compound 107(Table 1) at 130° C.

In a 100 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 1.759 g (4.36 mmol) of compound 107 and 45.45 g (436mmol) of styrene are mixed and degased. The clear solution obtained isheated under argon to 130° C. and polymerization is carried out during 6h. The reaction mixture is then cooled to 80° C. The remaining monomeris removed by evaporation under high vacuum to give 39 g (86%) of thepolystyrene.

Mn=7907, Mw=9162, PD=1.2

Example B8 Polymerization of styrene with 1 mol % of compound 108(Table 1) at 130° C.

In a 100 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 2.611 g (4.36 mmol) of compound 108 and 45.45 g (436mmol) of styrene are mixed and degased. The clear solution obtained isheated under argon to 130° C. and polymerization is carried out during 6h. The reaction mixture is then cooled to 80° C. The remaining monomeris removed by evaporation under high vacuum to give 39 g (86%) of thepolystyrene.

Mn=8616, Mw=9952, PD=1.2

Example B9 Polymerization of styrene with 1 mol % of compound 109(Table 1) at 130° C.

In a 100 ml three neck flask, equipped with thermometer, cooler andmagnetic stirrer, 1.511 g (4.36 mmol) of compound 109 and 45.45 g (436mmol) of styrene are mixed and degased. The clear solution obtained isheated under argon to 130° C. and polymerization is carried out during 6h. The reaction mixture is then cooled to 80° C. The remaining monomeris removed by evaporation under high vacuum to give 37.3 g (82%) of thepolystyrene.

Mn=7882, Mw=8820, PD=1.1

Example B10 Reinitiation of poly-styrene terminated with Compound 101with n-butylacrylate

In a dry, argon-purged Schlenk tube 2.5 g of polystyrene terminated withCompound 101 are dissolved in 15 g n-butylacrylate. The mixture isdegassed in three consecutive freeze-thaw-cycles and purged with argon.The stirred solution is then immersed in an oil bath and heated to 145°C. for 6 h. The residual monomer is then removed under vacuum at 40° C.and the blockcopolymer is dried at 40° C. in vacuum until constantweight is achieved. Conversion referred to the monomer (n-butylacrylate)is 36.2%. The molecular weight (M_(p)) increased from 9300 g/mol (Cmpd101-term-PS) to 47300 g/mol (PS-b-PBuA) and the polydispersity from 1.2to 1.8.

Example B11 Reinitiation of a poly-n-butylacrylate terminated withCompound 101 with styrene

In a dry, argon-purged Schlenk tube 2.5 g of poly-n-butylacrylateterminated with Compound 101 are dissolved in 15 g styrene. The mixtureis degassed in three consecutive freeze-thaw-cycles and purged withargon. The stirred solution is then immersed in an oil bath and heatedto 130° C. for 6 h. The residual monomer is then removed under vacuum at40° C. and the blockcopolymer is dried at 40° C. in vacuum untilconstant weight is achieved. Conversion referred to the monomer(styrene) is 66.0%. The molecular weight (M_(p)) increased from 8600g/mol (CG 41-0330-term-PBuA) to 47500 g/mol (PBuA-b-PS) and thepolydispersity from 1.3 to 1.5.

1. A compound of formula (I)

G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂ together andG₃ and G₄ together, or G₁ and G₂ together or G₃ and G₄ together arepentamethylene; wherein, when G₁, G₂, G₃ and G₄ are C₁–C₄alkyl, at leastone is higher alkyl than methyl; G₅ and G₆ are each independently of theother hydrogen or C₁–C₄alkyl; n is 1, 2, 3, or 4; Y is O or NR₂ or whenn is 1 and R₁ represents alkyl or aryl, Y is additionally a direct bond;R₂ is H, C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H, straight or branchedC₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, which may be unsubstitutedor substitued by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl; phenyl,C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or substitutedby one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substitued by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; if n is 4, R₁ is a tetravalent radical ofan aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; and X isselected from the group consisting of —CH₂-aryl,

 —CH₂—CH₂-aryl,

(C₅–C₆cycloalkyl)₂CCN, (C₁–C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁–C₁₂)alkyl-CR₂₀—C(O)—(C₁–C₁₂)alkyl,(C₁–C₁₂)alkyl-CR₂₀—C(O)—(C₆–C₁₀)aryl,(C₁–C₁₂)alkyl-CR₂₀—C(O)—(C₁–C₁₂)alkoxy, (C₁–C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁–C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁–C₁₂)alkyl,(C₁–C₁₂)alkyl-CR₂₀—CO—NH(C₁–C₁₂)alkyl, (C₁–C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

 3-cyclohexenyl, 3-cyclopentenyl,

 wherein R₂₀ is hydrogen or C₁–C₁₂alkyl; the alkyl groups areunsubstituted or substituted with one or more —OH, —COOH or —C(O)R₂₀groups; and the aryl groups are phenyl or naphthyl which areunsubstituted or substituted with C₁–C₁₂alkyl, halogen, C₁–C₁₂alkoxy,C₁–C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COO(C₁–C₁₂)alkyl.
 2. Acompound according to claim 1 wherein X is selected from the groupconsisting of —CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅–C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁–C₈alkyl)CR₂₀—C(O)-phenyl,(C₁–C₈)alkyl-CR₂₀—C(O)—(C₁–C₈)alkyl-CR₂₀—C(O)—(C₁–C₈)alkyl,(C₁–C₈)alkyl-CR₂₀—C(O)—N-di(C₁–C₈)alkyl,(C₁–C₈)alkyl-CR₂₀—C(O)—NH(C₁–C₈)alkyl and (C₁–C₈)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁–C₈)alkyl.
 3. A compound according toclaim 2 wherein X is selected from the group consisting of —CH₂-phenyl,CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅–C₈cycloalkyl)₂CCN, (CH₃)₂CCN, or

—CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁–C₄alkyl)CR₂₀—C(O)-phenyl,(C₁–C₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkyl,(C₁–C₄)alkyl-CR₂₀—C(O)—N-di(C₁–C₄)alkyl,(C₁–C₄)alkyl-CR₂₀—C(O)—NH(C₁–C₄)alkyl and (C₁–C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁–C₄)alkyl.
 4. A compound according toclaim 1 wherein at least one of G₁, G₂, G₃ and G₄ is ethyl and theothers are methyl and G₅ and G₆ are each independently of the otherhydrogen or methyl.
 5. A compound according to claim 1 wherein Y is O.6. A compound according to claim 1 wherein G₁ and G₃ are methyl and G₂and G₄ are ethyl, or G₁ and G₂ are methyl and G₃ and G₄ are ethyl; G₅and G₆ are each independently of the other hydrogen or methyl; and Y isO; n is 1, R₁ is H, straight or branched C₁–C₁₈alkyl or C₃–C₁₈alkenyl;C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl; phenyl, C₇–C₉phenylalkyl ornaphthyl which may be unsubstituted or substituted by one or moreC₁–C₈alkyl, halogen, OH or C₁–C₈alkoxy; or —C(O)—C₁–C₃₆alkyl, or an acylmoiety of a α,β-unsaturated carboxylic acid having 3 to 5 carbon atomsor of an aromatic carboxylic acid having 7 to 15 carbon atoms; and X isselected from the group consisting of —CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (C₅–C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

 —CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁–C₄alkyl)CR₂₀—C(O)-phenyl,(C₁–C₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkoxy,(C₁C₄)alkyl-CR₂₀—C(O)—(C₁–C₄)alkyl,(C₁–C₄)alkyl-CR₂₀—C(O)—N-di(C₁–C₄)alkyl,(C₁–C₄)alkyl-CR₂₀—C(O)—NH(C₁–C₄)alkyl and (C₁–C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁–C₄)alkyl.
 7. A compound according toclaim 1 which is a)2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oxime,b)2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-acetoximino-piperidine,c) 2,2-Diethyl-6,6-dimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oxime,d)2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-pivaloyloximino-piperidineor e)2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-4-benzoyloximino-piperidine.8. A polymerizable composition, comprising a) at least one ethylenicallyunsaturated monomer or oligomer, and b) a compound according to formula(I)

G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂ together andG₃ and G₄ together, or G₁ and G₂ together or G₃ and G₄ together arepentamethylene; G₅ and G₆ are each independently of the other hydrogenor C₁–C₄alkyl; and X represents a group such that the free radical X.derived from X is capable of initiating polymerization of ethylenicallyunsaturated monomers; n is 1, 2, 3, or 4; Y is O or NR₂ or when n is 1and R₁ represents alkyl, or aryl Y is additionally a direct bond; R₂ isH, C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H, straight or branchedC₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, which may be unsubstitutedor substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl; phenyl,C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or substitutedby one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C,₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
 9. Acomposition according to claim 8, wherein the ethylenically unsaturatedmonomer or oligomer is selected from the group consisting of ethylene,propylene, n-butylene, i-butylene, styrene, substituted styrene,conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone,vinylimidazole, maleic anhydride, (alkyl)acrylic acidanhydrides,(alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylonitriles,(alkyl)acrylamides, vinyl halides and vinylidene halides.
 10. Acomposition according to claim 8, wherein the initiator compound ispresent in an amount of from 0.01 mol-% to 20 mol-%, based on themonomer or monomer mixture.
 11. A process for preparing an oligomer, acooligomer, a polymer or a copolymer (block or random) by free radicalpolymerization of at least one ethylenically unsaturated monomer oroligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of an initiator compound of formula(I)

under reaction conditions capable of effecting scission of the O—C bondto form two free radicals, the radical .X being capable of initiatingpolymerization; where G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl orG₁ and G₂ together and G₃ and G₄ together, or G₁ and G₂ together or G₃and G₄ together are pentamethylene; G₅ and G₆ are each independently ofthe other hydrogen or C₁–C₄alkyl; and X represents a group such that thefree radical X. derived from X is capable of initiating polymerizationof ethylenically unsaturated monomers; n is 1, 2, 3, or 4; Y is O or NR₂or when n is 1 and R₁ represents alkyl or aryl, Y is additionally adirect bond; R₂ is H, C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H,straight or branched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, whichmay be unsubstituted or substituted by one or more OH, C₁–C₈alkoxy,carboxy or C₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxyor C₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
 12. Aprocess according to claim 11, wherein the scission of the O—C bond iseffected by ultrasonic treatment, heating or exposure to electromagneticradiation, ranging from γ to microwaves.
 13. A process according toclaim 11, wherein the scission of the O—C bond is effected by heatingand takes place at a temperature of between 50° C. and 160° C.
 14. Acompound according to formula (II)

G₁ and G₃ are independently C₁–C₄alkyl; G₂ and G₄ are independentlyC₂–C₄alkyl; G₅ and G₆ are each independently of the other hydrogen orC₁–C₄alkyl; n is 1, 2, 3, or 4, Y is O or NR₂; R₂ is H, C₁–C₁₈alkyl orphenyl; if n is 1, R₁ is H, straight or branched C₁–C₁₈alkyl,C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, which may be unsubstituted orsubstituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl; phenyl,C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or substitutedby one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
 15. Apolymerizable composition, comprising a) at least one ethylenicallyunsaturated monomer or oligomer, and b) a compound according to formula(II)

G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂ together andG₃ and G₄ together, or G₁ and G₂ together or G₃ and G₄ together arepentamethylene; G₅ and G₆ are each independently of the other hydrogenor C₁–C₄alkyl; n is 1, 2, 3, or 4; Y is O or NR₂ or when n is 1 and R₁represents alkyl or aryl, Y is additionally a direct bond; R₂ is H,C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H, straight or branchedC₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, which may be unsubstitutedor substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl; phenyl,C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or substitutedby one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; and c)source of free radicals.
 16. A composition according to claim 15,wherein the compound of formula (II) is present in an amount of from0.01 mol-% to 20 mol-%, based on the monomer or monomer mixture.
 17. Acomposition according to claim 15, wherein the free radical source ispresent in an amount of from 0.01 mol-% to 20 mol-%, based on themonomer or monomer mixture.
 18. A composition according to claim 15wherein the molar ratio of the radical source to the compound of formulaII may be from 1:10 to 10:1.
 19. A process for preparing an oligomer, acooligomer, a polymer or a copolymer (block or random) by free radicalpolymerization of at least one ethylenically unsaturated monomer oroligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of a compound of formula (II)

and a source of free radicals, the radials being capable of initiatingpolymerization; where G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl orG₁ and G₂ together and G₃ and G₄ together, or G₁ and G₂ together or G₃and G₄ together are pentamethylene; G₅ and G₆ are each independently ofthe other hydrogen or C₁–C₄alkyl; n is 1, 2, 3, or 4; Y is O or NR₂ orwhen n is 1 and R₁ represents alkyl or aryl, Y is additionally a directbond; R₂ is H, C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H, straight orbranched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl; phenyl,C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or substitutedby one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
 20. Apolymer prepared by radical polymerization according to claim 11 havingattached a group

where G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂together and G₃ and G₄ together, or G₁ and G₂ together or G₃ and G₄together are pentamethylene; G₅ and G₆ are each independently of theother hydrogen or C₁–C₄alkyl; and X represents a group such that thefree radical X. derived from X is capable of initiating polymerizationof ethylenically unsaturated monomers; n is 1, 2, 3, or 4; Y is O or NR₂or when n is 1 and R₁ represents alkyl or aryl, Y is additionally adirect bond; R₂ is H, C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H,straight or branched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, whichmay be unsubstituted or substituted by one or more OH, C₁–C₈alkoxy,carboxy or C₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxyor C₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
 21. Animproved process for the preparation of a compound of formula (I)

comprising reacting a compound of formula (X)

with a compound of formula (XI),R₁—Y—NH₂  (XI) characterized in that the compound of formula X isfirstly treated with an acid or base catalyst or the acid or basecatalyst is added during the imine forming reaction; where G₁, G₂, G₃and G₄ are independently C₁–C₄alkyl or G₁ and G₂ together and G₃ and G₄together, or G₁ and G₂ together or G₃ and G₄ together arepentamethylene; G₅ and G₆ are each independently of the other hydrogenor C₁–C₄alkyl; and X represents a group such that the free radical X.derived from X is capable of initiating polymerization of ethylenicallyunsaturated monomers; n is 1, 2, 3, or 4; Y is O or NR₂ or when n is 1and R₁ represents alkyl or aryl, Y is additionally a direct bond; R₂ isH, C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H, straight or branchedC₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, which may be unsubstitutedor substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl; phenyl,C₇–C₉phenylalkyl or naphthyl which may be unsubstituted or substitutedby one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
 22. Apolymer prepared by radical polymerization according to claim 19 havingattached a group

where G₁, G₂, G₃ and G₄ are independently C₁–C₄alkyl or G₁ and G₂together and G₃ and G₄ together, or G₁ and G₂ together or G₃ and G₄together are pentamethylene; G₅ and G₆ are each independently of theother hydrogen or C₁–C₄alkyl; and X represents a group such that thefree radical X. derived from X is capable of initiating polymerizationof ethylenically unsaturated monomers; n is 1, 2, 3, or 4; Y is O or NR₂or when n is 1 and R₁ represents alkyl or aryl, Y is additionally adirect bond; R₂ is H, C₁–C₁₈alkyl or phenyl; if n is 1, R₁ is H,straight or branched C₁–C₁₈alkyl, C₃–C₁₈alkenyl or C₃–C₁₈alkinyl, whichmay be unsubstituted or substituted by one or more OH, C₁–C₈alkoxy,carboxy or C₁–C₈alkoxycarbonyl; C₅–C₁₂cycloalkyl or C₅–C₁₂cycloalkenyl;phenyl, C₇–C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁–C₈alkyl, halogen, OH, C₁–C₈alkoxy, carboxyor C₁–C₈alkoxycarbonyl; —C(O)—C₁–C₃₆alkyl, or an acyl moiety of aα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Q⁺,—PO(O⁻Q⁺)₂, —P(O)(OR₂)_(2,)—SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂ or Si(Me)₃,wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; if n is 2, R₁ isC₁–C₁₈alkylene, C₃–C₁₈alkenylene or C₃–C₁₈alkinylene, which may beunsubstituted or substituted by one or more OH, C₁–C₈alkoxy, carboxy orC₁–C₈alkoxycarbonyl; or xylylene; or R₁ is a bisacyl radical of analiphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon atoms;if n is 3, R₁ is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid; and if n is 4, R₁ is a tetravalent radicalof an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.